CN108997418B - Improved technology for synthesizing omethoate - Google Patents
Improved technology for synthesizing omethoate Download PDFInfo
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- CN108997418B CN108997418B CN201810886441.4A CN201810886441A CN108997418B CN 108997418 B CN108997418 B CN 108997418B CN 201810886441 A CN201810886441 A CN 201810886441A CN 108997418 B CN108997418 B CN 108997418B
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- PZXOQEXFMJCDPG-UHFFFAOYSA-N omethoate Chemical compound CNC(=O)CSP(=O)(OC)OC PZXOQEXFMJCDPG-UHFFFAOYSA-N 0.000 title claims abstract description 89
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 12
- 238000005516 engineering process Methods 0.000 title description 3
- 239000010779 crude oil Substances 0.000 claims abstract description 72
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims abstract description 54
- 150000002148 esters Chemical class 0.000 claims abstract description 48
- 238000000034 method Methods 0.000 claims abstract description 46
- 238000006243 chemical reaction Methods 0.000 claims abstract description 43
- -1 oxygen sulfur phospholipid Chemical class 0.000 claims abstract description 36
- 230000008569 process Effects 0.000 claims abstract description 33
- 238000001035 drying Methods 0.000 claims abstract description 32
- 235000019270 ammonium chloride Nutrition 0.000 claims abstract description 27
- 239000006227 byproduct Substances 0.000 claims abstract description 13
- 238000005576 amination reaction Methods 0.000 claims abstract description 4
- 239000000463 material Substances 0.000 claims description 49
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 26
- 239000007788 liquid Substances 0.000 claims description 22
- 238000003786 synthesis reaction Methods 0.000 claims description 22
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 18
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 18
- 230000015572 biosynthetic process Effects 0.000 claims description 18
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 14
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 claims description 14
- 238000007599 discharging Methods 0.000 claims description 14
- 238000004321 preservation Methods 0.000 claims description 14
- 238000005086 pumping Methods 0.000 claims description 14
- 238000000605 extraction Methods 0.000 claims description 13
- QABLOFMHHSOFRJ-UHFFFAOYSA-N methyl 2-chloroacetate Chemical compound COC(=O)CCl QABLOFMHHSOFRJ-UHFFFAOYSA-N 0.000 claims description 13
- 238000003860 storage Methods 0.000 claims description 12
- 230000001502 supplementing effect Effects 0.000 claims description 12
- 239000002808 molecular sieve Substances 0.000 claims description 11
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 11
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical group [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 9
- 229910021529 ammonia Inorganic materials 0.000 claims description 9
- RYYWUUFWQRZTIU-UHFFFAOYSA-K thiophosphate Chemical compound [O-]P([O-])([O-])=S RYYWUUFWQRZTIU-UHFFFAOYSA-K 0.000 claims description 9
- 239000002274 desiccant Substances 0.000 claims description 8
- 239000007864 aqueous solution Substances 0.000 claims description 7
- 239000000706 filtrate Substances 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- INZKVSHWMKMVQE-UHFFFAOYSA-N OP(O)(O)=O.O.S Chemical compound OP(O)(O)=O.O.S INZKVSHWMKMVQE-UHFFFAOYSA-N 0.000 claims description 6
- 239000000498 cooling water Substances 0.000 claims description 6
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 5
- IVTHSFJXIARUFL-UHFFFAOYSA-N triazanium;thiophosphate Chemical compound [NH4+].[NH4+].[NH4+].[O-]P([O-])([O-])=S IVTHSFJXIARUFL-UHFFFAOYSA-N 0.000 claims description 5
- 239000003054 catalyst Substances 0.000 claims description 4
- CZHYKKAKFWLGJO-UHFFFAOYSA-N dimethyl phosphite Chemical compound COP([O-])OC CZHYKKAKFWLGJO-UHFFFAOYSA-N 0.000 claims description 3
- 230000006872 improvement Effects 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- 230000009469 supplementation Effects 0.000 claims description 2
- 239000000047 product Substances 0.000 abstract description 8
- 230000007062 hydrolysis Effects 0.000 abstract description 5
- 238000006460 hydrolysis reaction Methods 0.000 abstract description 5
- 230000008901 benefit Effects 0.000 abstract description 4
- 150000003839 salts Chemical class 0.000 abstract description 3
- 150000001875 compounds Chemical class 0.000 abstract description 2
- 238000002360 preparation method Methods 0.000 description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 13
- 150000002894 organic compounds Chemical class 0.000 description 8
- 238000007086 side reaction Methods 0.000 description 6
- RYYWUUFWQRZTIU-UHFFFAOYSA-N Thiophosphoric acid Chemical class OP(O)(S)=O RYYWUUFWQRZTIU-UHFFFAOYSA-N 0.000 description 5
- 238000009826 distribution Methods 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- WJNVUXXUQLHUEU-UHFFFAOYSA-N OP(O)(O)=S.OP(O)(O)=S.O.O.O Chemical compound OP(O)(O)=S.OP(O)(O)=S.O.O.O WJNVUXXUQLHUEU-UHFFFAOYSA-N 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 241000258937 Hemiptera Species 0.000 description 2
- QLULGSLAHXLKSR-UHFFFAOYSA-N azane;phosphane Chemical compound N.P QLULGSLAHXLKSR-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 241001124076 Aphididae Species 0.000 description 1
- 241001600408 Aphis gossypii Species 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- 206010059866 Drug resistance Diseases 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 241000488583 Panonychus ulmi Species 0.000 description 1
- 240000000111 Saccharum officinarum Species 0.000 description 1
- 235000007201 Saccharum officinarum Nutrition 0.000 description 1
- 240000006394 Sorghum bicolor Species 0.000 description 1
- 235000011684 Sorghum saccharatum Nutrition 0.000 description 1
- 235000021307 Triticum Nutrition 0.000 description 1
- 244000098338 Triticum aestivum Species 0.000 description 1
- 241000607479 Yersinia pestis Species 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000000895 acaricidal effect Effects 0.000 description 1
- 239000000642 acaricide Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- HTZCNXWZYVXIMZ-UHFFFAOYSA-M benzyl(triethyl)azanium;chloride Chemical compound [Cl-].CC[N+](CC)(CC)CC1=CC=CC=C1 HTZCNXWZYVXIMZ-UHFFFAOYSA-M 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- WOWHHFRSBJGXCM-UHFFFAOYSA-M cetyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCC[N+](C)(C)C WOWHHFRSBJGXCM-UHFFFAOYSA-M 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000002917 insecticide Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 238000006053 organic reaction Methods 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000009885 systemic effect Effects 0.000 description 1
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/06—Phosphorus compounds without P—C bonds
- C07F9/16—Esters of thiophosphoric acids or thiophosphorous acids
- C07F9/165—Esters of thiophosphoric acids
- C07F9/1651—Esters of thiophosphoric acids with hydroxyalkyl compounds with further substituents on alkyl
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
Abstract
The invention discloses an improved process for synthesizing omethoate, which comprises the steps of drying crude omethoate prepared by a post-amination method, and then desolventizing to prepare the omethoate crude oil. The invention improves a plurality of processes, improves the reaction environment to the maximum extent, improves the progress of the main reaction, reduces the hydrolysis, improves the reaction yield, and leads the post-treatment of the salt-containing compound to be more convenient. By using the process, the yield of the refined ester of the oxygen sulfur phospholipid can be improved to over 86 percent, and the purity can be improved to over 90 percent; the purity of the ammonium chloride can reach more than 99 percent, the ammonium chloride can be directly sold as a first-grade product of a byproduct, and the total yield of the omethoate crude oil can be improved to more than 79 percent; the purity of the crude oil is also improved, the whole process is greatly improved, and the social and economic benefits are huge.
Description
Technical Field
The invention relates to an improved process for synthesizing omethoate, belonging to the technical field of organic matter synthesis.
Background
Organic synthesis is a common reaction, but problems occur in the organic synthesis process due to the self-reaction of organic synthesis. For example, in the solid-liquid organic synthesis reaction, many side reactions occur, most commonly by-products containing salts, and the occurrence of the side reactions has more or less certain influence on the main reaction, such as: influence the progress of the main reaction, influence the content, yield and the like of the main product. If the organic compound is hydrolyzed, the content and yield of the product are adversely affected.
Omethoate is a high-efficiency systemic insecticide and acaricide, is widely applied to crops such as rice, cotton, fruit trees, wheat, sorghum, sugarcane and the like, is used for preventing and controlling sucking pests, and has special effects on red spiders, aphids, cotton aphids, whiteflies, scale insects and the like with drug resistance. At present, omethoate is prepared by adopting a post-amination method in China, but problems also exist in the omethoate synthesis process. Such as ammonium chloride, is produced as a byproduct in the reaction of oxaphosphoesters in the synthesis of omethoate. In the traditional process of the reaction, water needs to be added, the reaction is carried out at 65 ℃, the whole process environment is particularly favorable for dissolving ammonium chloride in a crude ester system, so that the system heat release is large, workers have difficulty in operating the temperature, the side reaction is increased, the chance of seeing main and side products is increased to a greater extent, and the yield of the step is reduced. For example, omethoate crude oil needs to be desolventized, and omethoate is hydrolyzed in the process, so that the yield and the content of the omethoate crude oil are reduced.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide an improved process for synthesizing omethoate, which has the advantages of more convenient temperature control, high product purity and high yield.
In order to achieve the purpose, the invention adopts the technical scheme that:
an improved process for synthesizing omethoate comprises the following steps: in the process of preparing the omethoate by adopting the post-amination method, the prepared omethoate crude oil is dried and then desolventized to prepare the omethoate crude oil.
The drying is three-stage drying.
The improved process of omethoate mainly comprises the following steps: (1) preparing coarse ester of oxygen sulfur phosphate; (2) preparing refined ester of oxygen sulfur phosphate; (3) preparing omethoate crude oil; (4) extracting omethoate crude oil; (5) drying the omethoate crude oil; (6) and (3) preparing omethoate refined crude oil.
The preparation of the coarse ester of the oxygen sulfur phospholipid in the step (1) is an anhydrous system, the reaction temperature is 45-55 ℃, and the reaction time is 2-4 h.
The specific method for preparing the coarse ester of the oxygen sulfur phospholipid in the step (1) comprises the following steps: sequentially adding 1200kg of methyl chloroacetate, 500L of sulfur and phosphorus ammonium salt and 2-5kg of catalyst into a reaction kettle, starting a stirring and steam valve, closing the steam valve when the temperature rises to 45-55 ℃, preserving the heat at 45-55 ℃ for 2-4h, opening a cooling water valve after the heat preservation is finished to cool the materials, discharging the materials when the temperature is reduced to 20-40 ℃, and centrifugally separating ammonium chloride from the materials to obtain a thrown filtrate, namely the coarse oxygen sulfur phosphate ester; and drying the centrifuged ammonium chloride to obtain a byproduct for sale.
The specific method for preparing the oxygen sulfur phospholipid refined ester in the step (2) comprises the following steps: firstly, drying the crude ester of the oxygen sulfur phospholipid, and then desolventizing to prepare the refined ester of the oxygen sulfur phospholipid.
The specific method for preparing the omethoate crude oil in the step (3) comprises the following steps: adding 500-600kg of thiophosphate refined ester into a synthesis pot, dropping 170-230kg of monomethylamine aqueous solution with the mass fraction of 40% when the temperature of the synthesis pot is reduced to-25 ℃, and controlling the dropping temperature to be-9 to-12 ℃; after the dropwise addition, preserving heat for 20-40min at-8 to-12 ℃, adding hydrochloric acid to adjust the pH value to 5-7 after the heat preservation is finished, controlling the temperature at 0 ℃, supplementing 300-600kg of chloroform, and pumping the feed liquid into a material separating tank for subsequent extraction after the supplementation.
The drying agent is a 3A molecular sieve, and the weight ratio of the molecular sieve to the substances to be dried is 1: 2; the catalyst is one or a mixture of more of tributylamine, triethylamine, TEBA and hexadecyl trimethyl ammonium chloride; the desolventizing temperature is controlled at 70-90 ℃, and the vacuum is controlled below-0.095 MPa.
The method for synthesizing omethoate comprises the following steps:
(1) preparation of crude ester of oxathiophosphate
Sequentially adding 1200kg of methyl chloroacetate, 500L of sulfur and phosphorus ammonium salt and 2-5kg of catalyst into a reaction kettle, starting a stirring and steam valve, closing the steam valve when the temperature rises to 45-55 ℃, preserving the heat at 45-55 ℃ for 2-4h, opening a cooling water valve after the heat preservation is finished to cool the materials, discharging the materials when the temperature is reduced to 20-40 ℃, and centrifugally separating ammonium chloride from the materials to obtain a thrown filtrate, namely the coarse oxygen sulfur phosphate ester; drying the centrifuged ammonium chloride and selling a byproduct;
(2) preparation of refined phosphorothioates
Carrying out three-stage drying on the oxygen thiophosphate crude ester by using a molecular sieve, putting the dried oxygen thiophosphate crude ester into a desolventizing pot for desolventizing, controlling the desolventizing temperature to be 100-plus 130 ℃ and the vacuum to be below-0.095 MPa, and removing methyl chloroacetate to obtain oxygen thiophosphate refined ester;
(3) preparation of omethoate crude oil
Adding 500-600kg of thiophosphate refined ester into a synthesis pot, dropping 170-230kg of monomethylamine aqueous solution with the mass fraction of 40% when the temperature of the synthesis pot is reduced to-25 ℃, and controlling the dropping temperature to be-9 to-12 ℃; after the dropwise addition is finished, preserving the heat at the temperature of-8 to-12 ℃ for 20-40min, adding hydrochloric acid to adjust the pH value to 5-7 after the heat preservation is finished, controlling the temperature at 0 ℃, supplementing 300 and 600kg of chloroform, and pumping the feed liquid into a material distributing tank after the supplementing;
(4) extraction of omethoate crude oil
Standing the feed liquid in a material separating tank for 20-40min, separating the lower layer material into a crude oil storage tank, performing chloroform extraction on the upper layer material for three times, and separating the extracted lower layer material into the crude oil storage tank;
(5) drying of omethoate crude oil
Carrying out three-stage drying on the omethoate crude oil by adopting a molecular sieve;
(6) preparation of omethoate refined crude oil
And (3) pumping the dried crude omethoate into a desolventizing kettle for desolventizing, controlling the desolventizing temperature to be 70-90 ℃, controlling the vacuum to be below-0.095 MPa, and discharging the crude omethoate after the vacuum is pulled for more than 20min to obtain the omethoate refined crude oil.
The preparation method of the ammonium thiophosphoryl salt comprises the following steps: pumping 600-plus 900L dimethyl phosphite into a reaction kettle, adding 80-150kg of sulfur powder, starting ammonia introduction when the temperature of the reaction kettle reaches below 5 ℃, stopping ammonia introduction when the ammonia introduction temperature is not more than 12 ℃, controlling the temperature to be 0-10 ℃ when the pH of reaction feed liquid is 6-7.5, preserving the temperature for 45-60min, and discharging.
The invention has the beneficial effects that:
1. according to the invention, the omethoate synthesis process is explored, and a certain degree of hydrolysis can occur in the omethoate desolventizing process, so that the purity and yield of omethoate are influenced. Therefore, the invention determines that the content of water in the reaction system has the greatest influence on the hydrolysis of the omethoate desolventizing process through a series of experiments. In order to effectively reduce hydrolysis in the organic compound desolventizing process, the omethoate crude oil needing to be desolventized is dried and dewatered, so that the whole system is anhydrous. Meanwhile, the invention repeatedly screens the drying agent of the liquid organic compound: (1) the drying of liquid organic compounds, generally by adding a drying agent to the liquid organic compound, must be carried out without chemical or catalytic interaction with the organic compound. (2) The drying agent should be insoluble in the liquid organic compound. (3) When selecting a desiccant that combines with water to form a hydrate, the water absorption capacity and drying effectiveness of the desiccant must be considered. Therefore, the method finally selects the 3A molecular sieve as the drying agent to dry the omethoate crude oil, and after the process is implemented, the total yield of the omethoate crude oil can be improved to more than 79%; the purity of the crude oil is also improved, and the whole process is greatly improved.
2. The invention also adopts a molecular sieve to dry the coarse oxygen-sulfur-phosphorus ester in the preparation process of the fine oxygen-sulfur-phosphorus ester, and obtains better effect, after the water of the coarse oxygen-sulfur-phosphorus ester is removed, the yield of the fine oxygen-sulfur-phosphorus ester can be improved to more than 86 percent, and the purity can be improved to more than 90 percent; and the purity of the ammonium chloride can reach more than 99 percent, and the ammonium chloride can be directly sold as a first-grade product of a byproduct. Compared with the traditional process, the overall process is greatly improved.
3. The invention develops an anhydrous reaction according to the characteristics of ammonium chloride (dissolution in water and precipitation at low temperature), namely, in the solid-liquid organic reaction generated by ammonium chloride as a side reaction, the water is prevented from entering, so that the whole system is in an anhydrous reaction state. Once the reaction system has no water, the ammonium chloride exists in the system in a solid state, and the overall process advantage is obvious according to the process improvement of the following three aspects:
(1) the amount of solvent is increased. The invention increases the proportion of the solvent (methyl chloroacetate), thereby increasing hot melting, and operators can better control the reaction temperature, thereby improving the reaction rate of reactants, increasing the generation of main products, reducing the molecular collision chance of byproducts and main products, and reducing the generation of side reactions.
(2) The reaction temperature was lowered. Because the system does not contain water, the reaction temperature is reduced compared with the reaction temperature when water exists, thereby reducing the reaction condition. In addition, the reduction of the reaction temperature not only can reduce the generation of side reactions, but also can improve the content of main products and the yield of the whole reaction.
(3) And adding a centrifugal and drying device. And after the ammonium chloride is separated out, centrifuging and drying the ammonium chloride to collect the ammonium chloride, recovering the filtrate as a solvent, and selling the dried ammonium chloride. The system does not add water, reduces the discharge of waste water, promotes the clean production of the company, increases the income of byproducts for the company, and achieves multiple purposes.
4. The invention improves a plurality of processes, improves the reaction environment to the maximum extent, improves the process of the main reaction, reduces the hydrolysis, improves the reaction yield, and ensures that the post-treatment of the salt-containing compound is more convenient and has great social and economic benefits.
Detailed Description
The following examples further illustrate the embodiments of the present invention in detail.
The preparation method of the ammonium thiophosphoryl salt comprises the following steps: pumping 700L dimethyl phosphite into a reaction kettle, adding 100kg of sulfur powder, starting ammonia introduction when the temperature of the reaction kettle reaches below 3 ℃, stopping ammonia introduction when the temperature in the reaction kettle is not more than 12 ℃ when the ammonia introduction is carried out, controlling the temperature to be 5 ℃, preserving the temperature for 50min when the pH of reaction feed liquid is 7.2, and discharging.
Example 1
An improved process for synthesizing omethoate, comprising the steps of:
(1) preparation of crude ester of oxathiophosphate
Adding 900kg of methyl chloroacetate, 500L of ammonium thiophosphate and 2.5kg of triethylamine into a reaction kettle in sequence, starting a stirring and steam valve, closing the steam valve when the temperature rises to 45 ℃, preserving the heat at 45 ℃ for 3 hours, opening a cooling water valve after the heat preservation is finished to cool the materials, discharging the materials when the temperature is reduced to 30 ℃, carrying out centrifugal separation on the materials, and obtaining the thrown filtrate, namely the coarse oxygen thiophosphate ester; drying the centrifuged ammonium chloride and selling a byproduct;
(2) preparation of refined phosphorothioates
Carrying out three-stage drying on the oxygen sulfur phospholipid crude ester by using a 3A molecular sieve, wherein the weight ratio of the molecular sieve to the oxygen sulfur phospholipid crude ester is 1: 2, putting the dried crude ester of the oxygen sulfur phospholipid into a desolventizing pot for desolventizing, controlling the desolventizing temperature to be 110 ℃ and the vacuum to be below-0.095 MPa, and removing methyl chloroacetate to obtain refined ester of the oxygen sulfur phospholipid;
(3) preparation of omethoate crude oil
Putting 500kg of thiophosphate refined ester into a synthesis pot, dropping 190kg of monomethylamine aqueous solution with mass fraction of 40% when the temperature of the synthesis pot is reduced to-25 ℃, and controlling the dropping temperature to be-10 ℃; after the dropwise addition is finished, preserving heat at-10 ℃ for 30min, adding hydrochloric acid to adjust the pH to 6 after the heat preservation is finished, controlling the temperature at 0 ℃, supplementing 300kg of chloroform, and pumping the feed liquid into a material distribution tank after the supplementing;
(4) extraction of omethoate crude oil
Standing the feed liquid in a material separating tank for 30min, separating the lower layer material into a crude oil storage tank, performing chloroform extraction on the upper layer material for three times, and separating the extracted lower layer material into the crude oil storage tank;
(5) drying of omethoate crude oil
Carrying out three-stage drying on the omethoate crude oil by adopting a 3A molecular sieve, wherein the weight ratio of the molecular sieve to the omethoate crude oil is 1: 2;
(6) preparation of omethoate refined crude oil
And (3) pumping the dried crude omethoate oil into a desolventizing kettle for desolventizing, controlling the desolventizing temperature to be 80 ℃, controlling the vacuum to be below-0.095 MPa, and vacuumizing for more than 30min, and discharging to obtain the omethoate crude oil.
The purity of the refined phosphorothioate ester obtained in this example was 89.78%, the yield was 85.89%, the purity of ammonium chloride was 99.07%, the purity of omethoate crude oil (refined) was 84.27%, and the total yield was 78.49%.
Example 2
An improved process for synthesizing omethoate, comprising the steps of:
(1) preparation of crude ester of oxathiophosphate
Putting 1200kg of methyl chloroacetate, 900L of ammonium thiophosphate and 3.5kg of triethylamine into a reaction kettle in sequence, starting a stirring and steam valve, closing the steam valve when the temperature rises to 55 ℃, preserving the heat at 55 ℃ for 3 hours, opening a cooling water valve after the heat preservation is finished to cool the materials, discharging the materials when the temperature is reduced to 30 ℃, carrying out centrifugal separation on ammonium chloride on the materials, and obtaining the thrown filtrate, namely the coarse oxygen thiophosphate ester; drying the centrifuged ammonium chloride and selling a byproduct;
(2) preparation of refined phosphorothioates
Carrying out three-stage drying on the oxygen sulfur phospholipid crude ester by using a 3A molecular sieve, wherein the weight ratio of the molecular sieve to the oxygen sulfur phospholipid crude ester is 1: 2, putting the dried crude ester of the oxygen sulfur phospholipid into a desolventizing pot for desolventizing, controlling the desolventizing temperature to be 130 ℃ and the vacuum to be below-0.095 MPa, and removing methyl chloroacetate to obtain refined ester of the oxygen sulfur phospholipid;
(3) preparation of omethoate crude oil
580kg of thiophosphate refined ester is put into a synthesis pot, 210kg of monomethylamine aqueous solution with the mass fraction of 40 percent is dripped when the temperature of the synthesis pot is reduced to minus 25 ℃, and the temperature during dripping is controlled to be minus 10 ℃; after the dropwise addition is finished, preserving heat at-10 ℃ for 30min, adding hydrochloric acid to adjust the pH to 6 after the heat preservation is finished, controlling the temperature at 0 ℃, supplementing 600kg of chloroform, and pumping the feed liquid into a material distribution tank after the supplementing;
(4) extraction of omethoate crude oil
Standing the feed liquid in a material separating tank for 30min, separating the lower layer material into a crude oil storage tank, performing chloroform extraction on the upper layer material for three times, and separating the extracted lower layer material into the crude oil storage tank;
(5) drying of omethoate crude oil
Carrying out three-stage drying on the omethoate crude oil by adopting a 3A molecular sieve, wherein the weight ratio of the molecular sieve to the omethoate crude oil is 1: 2;
(6) preparation of omethoate refined crude oil
And (3) pumping the dried crude omethoate oil into a desolventizing kettle for desolventizing, controlling the desolventizing temperature to be 85 ℃, controlling the vacuum to be below-0.095 MPa, and vacuumizing for more than 40min, and discharging to obtain the omethoate crude oil.
The purity of the phosphorothioate refined ester obtained in the example is 89.91%, the yield is 86.08%, the purity of ammonium chloride is 99.17%, the purity of omethoate crude oil is 84.75%, and the total yield is 78.93%.
Example 3
An improved process for synthesizing omethoate, comprising the steps of:
(1) preparation of crude ester of oxathiophosphate
Adding 1000kg of methyl chloroacetate, 700L of ammonium thiophosphate and 4kg of triethylamine into a reaction kettle in sequence, starting a stirring valve and a steam valve, closing the steam valve when the temperature rises to 50 ℃, preserving the heat at 50 ℃ for 3 hours, opening a cooling water valve after the heat preservation is finished to cool the materials, discharging the materials when the temperature is reduced to 30 ℃, carrying out centrifugal separation on the materials, and obtaining the thrown filtrate, namely the coarse oxygen thiophosphate ester; drying the centrifuged ammonium chloride and selling a byproduct;
(2) preparation of refined phosphorothioates
Carrying out three-stage drying on the oxygen sulfur phospholipid crude ester by using a 3A molecular sieve, wherein the weight ratio of the molecular sieve to the oxygen sulfur phospholipid crude ester is 1: 2, putting the dried crude ester of the oxygen sulfur phospholipid into a desolventizing pot for desolventizing, controlling the desolventizing temperature to be 120 ℃ and the vacuum to be below-0.095 MPa, and removing methyl chloroacetate to obtain refined ester of the oxygen sulfur phospholipid;
(3) preparation of omethoate crude oil
580kg of thiophosphate refined ester is put into a synthesis pot, 230kg of monomethylamine aqueous solution with the mass fraction of 40 percent is dripped when the temperature of the synthesis pot is reduced to minus 25 ℃, and the temperature during dripping is controlled to be minus 12 ℃; after the dropwise addition is finished, preserving heat at-10 ℃ for 30min, adding hydrochloric acid to adjust the pH to 6 after the heat preservation is finished, controlling the temperature at 0 ℃, supplementing 500kg of chloroform, and pumping the feed liquid into a material distribution tank after the supplementing;
(4) extraction of omethoate crude oil
Standing the feed liquid in a material separating tank for 30min, separating the lower layer material into a crude oil storage tank, performing chloroform extraction on the upper layer material for three times, and separating the extracted lower layer material into the crude oil storage tank;
(5) drying of omethoate crude oil
Carrying out three-stage drying on the omethoate crude oil by adopting a 3A molecular sieve, wherein the weight ratio of the molecular sieve to the omethoate crude oil is 1: 2;
(6) preparation of omethoate refined crude oil
And (3) pumping the dried crude omethoate oil into a desolventizing kettle for desolventizing, controlling the desolventizing temperature to be 75 ℃, controlling the vacuum to be below-0.095 MPa, and discharging for more than 20min to obtain the omethoate crude oil.
The purity of the phosphorothioate refined ester obtained in the example is 90.14%, the yield is 86.28%, the purity of ammonium chloride is 99.26%, the purity of omethoate crude oil is 84.67%, and the total yield is 79.09%.
Comparative example
The existing technology for synthesizing omethoate comprises the following steps:
(1) preparation of crude ester of oxathiophosphate
Adding 600kg of methyl chloroacetate, 700L of ammonium thiophosphate, 300kg of water and 4kg of triethylamine into a reaction kettle in sequence, starting a stirring valve and a steam valve, closing the steam valve when the temperature rises to 65 ℃, preserving heat for 3h at 65 ℃, standing for 3h in a water separation tank after the heat preservation is finished, separating a lower-layer crude product into a metering tank, filtering and then desolventizing to obtain the thiophosphoryl ester;
(2) preparation of refined phosphorothioates
Putting the crude ester of the oxygen sulfur phospholipid into a desolventizing pot for desolventizing, controlling the desolventizing temperature to be 120 ℃ and the vacuum to be below-0.095 MPa, and removing methyl chloroacetate to obtain refined ester of the oxygen sulfur phospholipid;
(3) preparation of omethoate crude oil
580kg of thiophosphate refined ester is put into a synthesis pot, 230kg of monomethylamine aqueous solution with the mass fraction of 40 percent is dripped when the temperature of the synthesis pot is reduced to-25 ℃, and the dripping temperature is controlled to be-12 ℃; after the dropwise addition is finished, preserving heat at-10 ℃ for 30min, adding hydrochloric acid to adjust the pH to 6 after the heat preservation is finished, controlling the temperature at 0 ℃, supplementing 500kg of chloroform, and pumping the feed liquid into a material distribution tank after the supplementing;
(4) extraction of omethoate crude oil
Standing the feed liquid in a material separating tank for 30min, separating the lower layer material into a crude oil storage tank, performing chloroform extraction on the upper layer material for three times, and separating the extracted lower layer material into the crude oil storage tank;
(5) preparation of omethoate refined crude oil
And (3) feeding the omethoate crude oil into a desolventizing kettle for desolventizing, controlling the desolventizing temperature to be 75 ℃, controlling the vacuum to be below-0.095 MPa, and discharging for more than 20min to obtain the omethoate crude oil.
The purity of the refined ester of the oxa-thiophosphate obtained in the comparative example is 87.56%, the yield is 83.76%, the purity of the ammonium chloride is 96.64%, the purity of the omethoate crude oil is 83.24%, and the total yield is 75.60%.
The foregoing description is only a preferred embodiment of the present invention, and various modifications and changes will occur to those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (3)
1. An improved process for synthesizing omethoate is characterized in that in the process of preparing omethoate by adopting a post-amination method, prepared omethoate crude oil is dried firstly and then desolventized to prepare the omethoate crude oil, and the improved process mainly comprises the following steps:
(1) preparing coarse ester of oxygen sulfur phosphate; (2) preparing refined ester of oxygen sulfur phosphate; (3) preparing omethoate crude oil; (4) extracting omethoate crude oil; (5) drying the omethoate crude oil; (6) preparing omethoate refined crude oil;
the specific method for preparing the coarse ester of the oxygen sulfur phospholipid in the step (1) comprises the following steps: sequentially adding 1200kg of methyl chloroacetate, 500kg of 900L of ammonium thiophosphate and 2-5kg of triethylamine serving as a catalyst into a reaction kettle, starting a stirring valve and a steam valve, closing the steam valve when the temperature rises to 45-55 ℃, preserving the heat at 45-55 ℃ for 2-4h, opening a cooling water valve after the heat preservation is finished to cool the materials, discharging the materials when the temperature is reduced to 20-40 ℃, and centrifugally separating ammonium chloride from the materials, wherein the thrown filtrate is the coarse oxygen sulfur phosphate ester; drying the centrifuged ammonium chloride and selling a byproduct;
the specific method for preparing the oxygen sulfur phospholipid refined ester in the step (2) comprises the following steps: firstly, drying the crude ester of the oxygen sulfur phospholipid, and then desolventizing to prepare refined ester of the oxygen sulfur phospholipid;
the specific method for preparing the omethoate crude oil in the step (3) comprises the following steps: adding 500-600kg of thiophosphate refined ester into a synthesis pot, dropping 170-230kg of monomethylamine aqueous solution with the mass fraction of 40% when the temperature of the synthesis pot is reduced to-25 ℃, and controlling the dropping temperature to be-9 to-12 ℃; after the dropwise addition is finished, preserving the heat at the temperature of-8 to-12 ℃ for 20-40min, adding hydrochloric acid to adjust the pH to be =5-7 after the heat preservation is finished, controlling the temperature at 0 ℃, supplementing 300 and 600kg of chloroform, and pumping the feed liquid into a material separating tank for subsequent extraction after the supplementation;
the drying is three-stage drying; the drying agent is a 3A molecular sieve, and the weight ratio of the molecular sieve to the substances to be dried is 1: 2; the desolventizing temperature of the crude omethoate after drying is controlled to be 70-90 ℃, and the vacuum is controlled to be below-0.095 MPa.
2. The improvement as set forth in claim 1, characterized in that the desolventizing temperature after the step (2) of the crude ester of oxathiophosphate is dried is controlled at 100-130 ℃, and the vacuum is controlled below-0.095 MPa; the specific method for extracting the omethoate crude oil in the step (4) comprises the following steps: and (3) standing the feed liquid in a material separating tank for 20-40min, separating the lower layer material into a crude oil storage tank, performing chloroform extraction on the upper layer material for three times, and separating the extracted lower layer material into the crude oil storage tank.
3. The improved process of claim 2 wherein the ammonium thiophosphoryl salt is prepared by the steps of: pumping 600-plus 900L dimethyl phosphite into a reaction kettle, adding 80-150kg of sulfur powder, starting ammonia introduction when the temperature of the reaction kettle reaches below 5 ℃, stopping ammonia introduction when the ammonia introduction temperature is not more than 12 ℃, controlling the temperature to be 0-10 ℃ when the pH of reaction feed liquid is 6-7.5, preserving the temperature for 45-60min, and discharging.
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